Photopolymerization mechanism

The photopolymerization mechanism for the polymerization of NVK in the presence of 2,4,7-trifluorene postulates the formation of a dimer radical cation by a charge-transfer reaction. The dimer radical cation may then form cyclodimers, form cationic polymers, or polymerize by a free radical process [70]. 

Photopolymerization Mechanisms of Acrylates in Poly(Methyl Methacrylate) Films. Urano, Toshiyuki Ito, Hideki Takahama, Keiji Yamaoka, Tsuguo (Research Center, Mitsubishi Chemical Corporation, Yokohama, Japan 227). Polym. Adv. Technol. 1999, 10 (4), 201-205 (Eng.), John Wiley Sons Ltd. Photoinitiation processes for photopolymer coating layers were investigated with respect to quenching rates by a laser flash photolysis using a total reflection cell, as well as to the decompn.-quantum yield of a sensitizer dye and a radical-generating reagent hy a gel... 

The photopolymerization process taking place within a representative mixture of sensitizer, initiator, chain-transfer agent, and monomer, typical of positive Cromalin, has been studied in detail (41,42). The exact mechanism is still controversial, but a generalized reaction scheme can be postulated as follows, where L2 = biimidazole dimer, S = sensitizer, RH = chain-transfer agent, L2 = excited biimidazole dimer, L = biimidazole radical,... 

Li et al. [87,88] found that aniline will process the photopolymerization of AN either in N,N-dimethylformamide (DMF) solution or in bulk with a fair rate of polymerization only next to DMT. From UV spectra it is proved that aniline will form a CTC with AN. Using 313-nm radiation that CTC is excited to an exciplex and polymerization proceeds. N-methylaniline will polymerize AN similarly. The following mechanism was proposed ... 

The well-known photopolymerization of acrylic monomers usually involves a charge transfer system with carbonyl compound as an acceptor and aliphatic tertiary amine, triethylamine (TEA), as a donor. Instead of tertiary amine such as TEA or DMT, Li et al. [89] investigated the photopolymerization of AN in the presence of benzophenone (BP) and aniline (A) or N-methylaniline (NMA) and found that the BP-A or BP-NMA system will give a higher rate of polymerization than that of the well-known system BP-TEA. Still, we know that secondary aromatic amine would be deprotonated of the H-atom mostly on the N-atom so we proposed the mechanism as follows ... 

The polymers initiated by BP amines were found to contain about one amino end group per molecular chain. It is reasonable to consider that the combination of BP and such polymers will initiate further polymerization of vinyl monomers. We investigated the photopolymerization of MMA with BP-PMMA bearing an anilino end group as the initiation system and found an increase of the molecular weight from GPC and viscometrical measurement [91]. This system can also initiate the photopolymerization of AN to form a block copolymer, which was characterized by GPC, elemental analysis, and IR spectra. The mechanism proposed is as follows ... 

Polymers in Schemes 12 and 13 were the first examples of the preparation of pyridinium and iminopyridinium ylide polymers. One of the more recent contributions of Kondo and his colleagues [16] deals with the sensitization effect of l-ethoxycarbonyliminopyridinium ylide (IPYY) (Scheme 14) on the photopolymerization of vinyl monomers. Only acrylic monomers such as MMA and methyl acrylate (MA) were photoinitiated by IPYY, while vinylacetate (VA), acrylonitrile (AN), and styrene were unaffected by the initiator used. A free radical mechanism was confirmed by a kinetic study. The complex of IPYY and MMA was defined as an exciplex that served as a precursor of the initiating radical. This ylide is unique in being stabilized by the participation of a... 

Photopolymerization of MMA was also carried out in the presence of visible light (440 nm) using /3-PCPY as the photoinitiator at 30°C [20]. The initiator and monomer exponent values were calculated as 0.5 and 1.0, respectively, showing ideal kinetics. An average value of kp /kt was 4.07 x 10 L-mol -s . Kinetic data and ESR studies indicated that the overall polymerization takes place by a radical mechanism via triplet carbene formation, which acts as the sources of the initiating radical. 

The presence of one carbonyl group per oligomer molecule was also ascertained. The orange colour of the resin suggested that some minor event during the photopolymerization produced chromophores in small concentrations. The presence of furoin among the products corroborated the proposed mechanism, which was shown not to involve free radical chain reactions. 

Direct transformation from 2,5-DSP to poly-2,5-DSP through 2,5-DSP oligomer in the crystal is shown in Scheme 1. This new reaction was named a four-centre-type photopolymerization. As well as being the first example of a topochemical reaction in a pure sense, the four-centre-type photopolymerization of 2,5-DSP crystals was the first example of photopolymerization via a step-growth mechanism. 

After the discovery of the photopolymerization of 2,5-DSP crystals, several types of photoproducts were found, not only the linear polymers, but some other derivatives, e.g. the V-shaped dimer or cyclophane (Hasegawa and Hashimoto, 1992). The photopolymerization occurs in a step-growth mechanism by cyclobutane formation between the excited olefin and the olefin in the ground state. 

In 1957, Otsu and coworkers reported that the polymer obtained from St with 13 could induce the radical polymerization of second monomers leading to block copolymers [70-74]. Poly(St)-hZock-poly(MMA), poly(St)-hZock-poly (AN), poly(St)-Z Zock-poly(VAc), and poly(St)-hZock-poly(VA) were prepared from the end-functional poly(St) [75], In the photopolymerization of St and MMA with 13, it was also confirmed that the molecular weight of the polymers produced linearly increased with the reaction time, although the reaction mechanism was not ascertained at that time. Thereafter, the poly(St) produced with 13 was confirmed to have two DC end groups, which can further dissociate pho-tochemically [76]. 

It was confirmed that the resulting polymers obtained from the St polymerization with 13 induced further photopolymerization of MMA to produce a block copolymer, and the yield and molecular weight increased as a function of the polymerization time, similar to the results for the polymerization of MMA with 13, indicating that this block copolymerization also proceeds via a living radical polymerization mechanism [64]. Similar results were also obtained for the photoblock copolymerization of VAc. Thus, various kinds of two- or three-component block copolymers were prepared [157,158]. 

Photocrosslinking. The second class of photopolymer chemistry that is used in some commercial products is based on the reaction of unsaturated moieties attached to an organic polymer. These photopolymer materials include the [2+2] cycloaddition of the ethylenic groups in poly(vinyl cinnamate) polymers and in the newer styryl pyridinium (10) and thiazolium (77) derivatives of poly(vinyl alcohol). The main advantage of this chemistry is that, unlike free-radical photopolymerization, they are insensitive to the presence of oxygen. This photopolymer mechanism is principally used in applications employing a washout development process (e.g. resists). 

Once the reaction of DTC radicals with monomer is neglected, propagation of radicals follows the mechanism seen in other radical photopolymerizations ... 

Studies were performed to demonstrate the effects of process variables such as light intensity, cure time, initiator concentration, and fiber loading on the evolution of the mechanical properties of the polymers and composites. Even with moderate incident light intensities (less than 500 mW/cm2) and high fiber loadings (60 wt.% random fibers) the photopolymerizations proceed to completion in minutes and exhibit mechanical properties equivalent to samples prepared by traditional... 

General Electric Co.) were added to the acrylic and epoxy monomers, respectively, to initiate photopolymerization. The acrylic monomers that polymerized by a free-radical mechanism were irradiated under nitrogen. The output of the lamp measured at the substrate was about 4 mW/cm2 at 260 nm and about 11 mW/cm2 at 310 nm. 

Network formation by photopolymerization has been studied for tetraethyleneglycol diacrylate (TEGDA) using isothermal calorimetry (DSC), isothermal shrinkage measurement and dynamic mechanical thermal analysis (DMTA). Due to vitrification the polymerization does not go to completion at room temperature. The ultimate conversion as measured by DSC seems to depend on light intensity. This can be explained by the observed delay of shrinkage with respect to conversion. 

However, mechanical measurements show that especially at low intensities, the photopolymerization process continues for a considerable time at a rate which cannot be detected by DSC. At equal doses the temperatures of maximum mechanical loss, T(tan S ax), were observed to be the same. 

In this contribution we present results obtained with tetra-ethyleneglycol diacrylate (TEGDA). This compound was chosen since its polymer shows an easily discernible maximum in the mechanical losses as represented by tan 5 or loss modulus E" versus temperature when it is prepared as a thin film on a metallic substrate. When photopolymerized at room temperature it forms a densely crosslinked, glassy polymer, just as required in several applications. Isothermal vitrification implies that the ultimate conversion of the reactive double bonds is restricted by the diffusion-limited character of the polymerization in the final stage of the reaction. Therefore, the ultimate conversion depends strongly on the temperature of the reaction and so does the glass transition. 

The influence of fillers has been studied mostly at hl volume fractions (40-42). However, in addition, it is instructive to study low volume fractions in order to test conformity with theoretical predictions that certain mechanical properties should increase monotonlcally as the volume fraction of filler is Increased (43). For example, Einstein s treatment of fluids predicts a linear increase in viscosity with an increasing volume fraction of rigid spheres. For glassy materials related comparisons can be made by reference to properties which depend mainly on plastic deformation, such as yield stress or, more conveniently, indentation hardness. Measurements of Vickers hardness number were made after photopolymerization of the BIS-GMA recipe, detailed above, containing varying amounts of a sllanted silicate filler with particles of tens of microns. Contrary to expectation, a minimum value was obtained (44.45). for a volume fraction of 0.03-0.05 (Fig. 4). Subsequently, similar results (46) were obtained with all 5 other fillers tested (Table 1). 

The general approach of graded radiation exposure can also be used to examine light driven processes such as photopolymerization [19]. For example, Lin-Gibson and coworkers used this library technique to examine structure-property relationships in photopolymerized dimethacrylate networks [38] and to screen the mechanical and biocompatibility performance of photopolymerized dental resins [39]. In another set of recent studies, Johnson and coworkers combined graded light exposure with temperature and composition gradients to map and model the photopolymerization kinetics of acrylates, thiolenes and a series of co-monomer systems [40 2]. 

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